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Antimicrobial systems and

I their use in plastics
The range of antimicrobial products designed to meet the
needs of film, fibre and moulding manufacturers has devel-
oped significantly in recent years.These products are benefit-
ing antimicrobial chopping boards, kitchen wear, hosiery, car-
pets, hospital waste bags and refuse containers among others.
Julie Simmons of leading supplier of antimicrobial systems
Wells Plastics explains.

The aim of antimicrobial systems in plastic
products is to reduce microbe populations
both within the material and found at the
surface. The growth of micro-organisms on
an object can be unsightly, lead to odours
and increase the risk of cross contamina-
tion with the accompanying possibility of
transmitting infections. Reducing odours is
an attractive benefit for many applications,
such as clothing and waste containers. By
helping to keep microbe populations low
and so reduce the risk of cross contamina-
tion, antimicrobial products can offer hos-
pitals, food manufacturers and consumers
extra peace of mind. The use of an antimi-
crobial in a product provides additional
protection against micro-organisms and
must always be used together with good
hygiene practice. Potential end uses for
antimicrobial systems include fibres for
clothing, bedding and upholstery, film for
waste bags, mattress covers, packaging and
moulding applications from garden furni-
ture to bathroom fittings.
The use ofantimicrobials in the wide range
of polymers now available, such as poly-
olefins, styrenics and polyamides, has devel-
oped from their use in PVC and other sys-
tems. In plasticized PVC, for example, the
biocide is primarily present to protect the
material itself from degradation caused by
bacteria and fimgi growth. The plasticizer
can act as the carrier for the biocide and
this method of addition has enabled the use
of potent but volatile organic biocides such
as 10',10'-Oxybisphenoxyarsine (OBPA)
and 2-n-octyl-4-isothiazolin-3-one (OIT).
For polymers where the plasticizer cannot
be used as the carrier the antimicrobial
additive has to be added to the melt. This
means that the additives used, among other
properties, must be thermally stable at the
processing temperature as well as being bio-
logically active. The majority of biocides
used in PVC are not sufficiently heat stable
to enable their use in many other polymers.
A new range ofantimicrobial additives,
often originally designed for cosmetics, has
been developed for use in plastics. As well
as greater heat stability, these additives gen-
erally have lower toxicity to humans and
the environment, although they are less
potent biocides than OBPA, for example.
There are a number of additives available
that are suitable for melt processing that
exhibit a range of properties. This variance
in properties means that the correct choice
of additive system for a particular applica-
tion can be critical. Typical differences
include the rate of action, effectiveness
against different micro-organisms, required
addition level, thermal stability and anti-
wash characteristics.
The active component of an antimicrobial
system can either be essentially organic or
inorganic. Wells Plastics has developed a
number of masterbatches to meet different
requirements.
Organic systems
Organic systems are generally based on
small molecules that may contain a metal
ion. They are incompatible with the poly-
mer matrix and therefore diffuse to the sur-
face where they interact with micro-organ-
isms present. Equilibrium is reached
between the additive present at the surface
and that in the body of the polymer.
Further additive will only diffuse out of the
polymer when the surface is wiped or
washed, providing extended antimicrobial
performance with the additive in the poly-
mer acting as a reservoir.
The organic T-Series masterbatch systems
contain 2,4,4'-trichloro-2'-hydroxy diph-
enyl ether, which is a small, flat molecule.
The major benefits of the T-Series additive
include:
• Widespread use in toothpaste, mouth-
wash and cosmetics for many years
• Effective use against most common
bacteria
• Low toxicity - approved for use in oral
applications
• Quick and repeated availability at the
surface
• Expected full food contact approval
The T-Series is well suited to many poly-
olefin applications, particularly film and
mouldings. Other systems, including zinc
pyrithione and N-Butyl-1,2-benzisothiazo-
lin-3-one are currently under investigation.
Inorganic systems
Inorganic systems are based on metal ions,
stabilized in some way so that they are
unreactive until released in association with
another agent, such as moisture. The most
common metal ion used is silver, the
antimicrobial effect of which has been uti-
lized for centuries. Metal ions interact with
many aspects of microbe cellular activity,
primarily through interference with enzy-
matic action. The metal ions as the antimi-
crobial agent remain stored in the polymer,
only being released gradually to the sur-
face, providing continual and long lasting
antimicrobial activity.

PlasticsAdditives& Compounding October 2000

20

The Ionpure TM and J-Series masterbatches
are two inorganic antimicrobial products.
The antimicrobial activity of Ionpure
results from the presence of silver ions that
are encapsulated in a soluble glass matrix.
In the presence of moisture the outer layer
of the glass matrix is slowly dissolved and
silver ions released at the surface. The glass
matrix not only protects the silver ions
during processing but also its solubility can
be chemically changed to alter the rate of
silver ion release.
The main benefits of Ionpure indude:
• Excellent antibacterial performance
• Good antifungal action when used at
higher concentrations
• Heat resistant up to at least 500°C and
non-volatility
• Availability with different formula-
tions, particle sizes and rates of silver
ion release
• Low toxicity - approved for cosmetics
High level of heat stability
The high heat stability and controlled
release of the Ionpure systems make them
ideal for use in engineering polymers.
Suitable applications include polyester
fibres, styrenic and polyolefin mouldings
with long life spans, as well as medical
devices.
The J-Series ofmasterbatches also uses sil-
ver ions as the biologically active agent.
With this system the silver is present as a
compound stabilized by a chemical associa-
tion with an inert material. In the pres-
ence of moisture the silver dissociates,
releasing silver ions at the surface.
For the J-Series the advantages include:
• Effectiveness against a wide range of
bacteria, fungi and algae
• High activity and mobility
• Low toxicity - approved for cosmetics
and some food contact applications
• Constant silver level to provide pro-
longed periods of effect
• Small particle size
• Thermal stability to above thermoplastic
processing conditions and non-volatility
These properties make the J-Series ideally
suitable for polypropylene fibres and for
providing films with anti-fungal and anti-
algal protection. Also available are further
systems based on silver and on zinc.
A specialized product, Ceramite TM, has
Agsiest: S.aure~
/(
CONTROL
FILM
FILM
CONTAINING
T-SERJES
<)
Halo = 22 m m
also been developed that is specifically
effective against dust-mites. The link
between dust-mites and asthma, eczema,
"cold like" symptoms and other complaints
is well known. The allergic reaction to
dust-mites is believed to be reversible,
though not curable, and removal of the
allergen leads to a return to normality.
Ceramite can assist in this process through
its incorporation into products, such as
carpets and bedding, where dust-mites live
and breed. The active component of
Ceramite is a boron compound, which is
encased in a soluble glass matrix to protect
it during processing and control its release.
In the high humidity conditions needed
for dust-mite population growth the boron
compound is released from the polymer
and acts as a desiccant, decreasing the
moisture in the dust-mites' bodies so weak-
ening them. The Ceramite system has
similar advantages to Ionpure, such as low
toxicity, skin contact approval and stability
at elevated temperatures.
Processing
The production of antimicrobial master-
batch systems requires careful handling and
specialist compounding experience. By
their very nature antimicrobial additives
raise health and safety issues that the work
force have to be aware of and the plant
designed to cope with. Producing concen-
trates of these materials requires specifically
configured twin screw extruders, careful
Plastics Additives & Compounding October 2000
2I
Additives
E¢oli S.typlfinmriu=
~'i iTM
\
Halo= 16ram Halo= lOmm
temperature control and processing condi-
tions set to ensure excellent dispersion.
Test methods
Testing for antimicrobial activity is an
important area and with the large number
of test methods available, one that can lead
to confusion. Many of the procedures
commonly used were developed for PVC
products and as such are not always suit-
able for use with the new additives used in
other polymers. As the incorporation of
these additives into polymers is relatively
new there is not yet an internationally rec-
ognized standard test method. However,
with the European Biocides Directive com-
ing into force and the use of these systems
increasing a standard method is likely to be
established.
There are two main types ofantimicrobial
test methods used, the halo and the viable
count procedures. Small differences
between the methods, such as the initial
number of micro-organisms placed on the
sample and sample preparation, can have a
significant effect on the results. Care there-
fore needs to be taken when selecting the
methodology and comparing results if dif-
ferent test methods have been used.
In halo or zone of inhibition methods the
sample, for example a small piece of film, is
placed on an agar plate, inoculated with
the test micro-organism and incubated. A
control, containing no antimicrobial addi-
tive, is carried out at the same time. After
 Additives
1000000
100000
.|
10000
i! ooo
~' 100
10
Control TPU Film TPU Film with Ionpure
incubation the plates are examined for
growth. If the antimicrobial additive has
been effective, a clear zone of no growth
(the zone of inhibition) is seen around the
sample or no growth is seen above or below
the sample. The zone of inhibition can be
measured and this gives a qualitative
impression of how effective the additive is
against different micro-organisms. The for-
mation of a zone of inhibition is a result of
diffusion of the additive out of the sample
and through the agar. Therefore, the size of
the zone produced depends not just on the
biostatic effectiveness of the additive but
Plastics Additives & Compounding October 2000
~ama also on its rate of These test methods are quantitative -
measuring how effective the additive is
diffusion and this
makes it difficult to use against the test organism. The results are
the test to compare usually quoted as log or percentage reduc-
different additives. tion. While a halo test demonstrates that
Halo tests normally an additive works, a viable count test tells
you how well it works. Viable count meth-
I indicate biostatic
action, as within the ods tend to be used for additives that do
zone of inhibition the not readily diffuse across the agar or have a
micro-organisms could surface contact effect, such as many of the
.... still be alive but repro- inorganic antimicrobials. They can also be
duction has been inhib- used to provide time related data, showing
ited preventing them how quickly an additive has an effect.
from forming visible
colonies. In other words
the bacteria have not
Case studies
been killed (which Through its development work Wells
would be biocidal Plastics has gained experience of using
action), they have been antimicrobial systems in a variety of
prevented from repro- products. Both the effectiveness of the
ducing (biostatic antimicrobial systems and the use of dif-
action). Obviously if ferent test methods are illustrated in the
reproduction is being following three examples.
prevented eventually
the bacteria present will Polyethylene film containing 1% o f a
die and the total popu- T-Series masterbatch.
lation will decrease. In A control sample of polyethylene film
fact many of the (containing no T-Series) and film pro-
antimicrobial systems duced with 1% of a T-Series masterbatch
suitable for plastics are were tested using a halo test method.
actually biostatic in The films were tested against three
action and in addition bacteria, Staphylococcus aureus
'true kill' claims can be (S.aureus), Escherichia coli (E.coli) and
difficult to verify. Salmonella typhimurium (S.typhimuri-
With viable count test urn). The results (see figure 1) show that
methods, the actual the film containing T-Series is effective
number of micro- against the three bacteria. They also
organism colonies are demonstrate that the effectiveness of a
counted. An inoculum system varies against different bacteria.
broth, which is a Sufficient additive was present in the
growth medium con- film to control all three test organisms,
taining the test micro- but the difference in the size of the halo
organisms, is produced and the number of produced indicates that different concen-
organisms initially present counted. The trations of the antimicrobial are needed
broth is used to inoculate the test sample to achieve this. S.aureus with the largest
and a control (containing no antimicrobial halo is more susceptible to the additive
additive), which together with the inocu- than E.coli, and S.typhimurium with the
lum broth are then incubated. After the smallest halo requires the highest con-
incubation period the micro-organisms are centration of additive to be controlled.
washed off the samples and the number of
micro-organisms still viable and able to TPU £dm containing 2% of an Ionpure
grow are counted. Results for the control masterbatch.
show the micro-organism growth possible TPU film for mattress covers, containing
on the plastic item and those for the test Ionpure, together with a control TPU
sample demonstrate the effect of the film, were tested using the viable count
antimicrobial additive. Japanese Film Sealing method.
22
 Additives
film, while the film containing Ionpure
10000000 -* 3% J-Series had significantly fewer bacteria present.
1000000 Control (0% J-Series)
Polypropylene fibres containing 3% of a
100000 2m
J-Series masterbatch
Polypropylene fibre samples were prduced
i~ 10000
containing 3% of a J-Series masterbatch.
1000
Together with control fibres containing no
100 J-Series, they were tested against a mixed
10 inoculum of S.aureus and E.coli using a
"2 .... ~ 0 viable count method. Counts were done
Baseline 0 hr 6 hr 24 hr 48 hr 7 day after five time periods, providing data on
Time how quickly the antimicrobial effect was
achieved and maintained. Figure 3 demon-
strates the effectiveness of the J-Series, with
The mattress covers were for use in hospi- control its spread. The graph in figure 2 reductions compared to the control of97%
tals so it was important that the product be shows that 24 hours after inoculation the after 6 hours and 99.9% after 24 hours. It
effective against MethiciUin Resistant control film has over 100 thousand bac- is interesting that between 48 hours and 7
Staphylococcus aureus (MRSA). MRSA teria present on it, while the test sample days bacterial growth occurred on the con-
is a strain of S.aureus that is resistant to containing Ionpure after the same period trol while on the J-Series fibres the bacteria
many antibiotics, and if wounds become has just under one thousand bacteria pres- count remained very low, equivalent to a
infected with it, the infection can be seri- ent. This demonstrates that the film con- 99.999% reduction. •
ous and even fatal. Therefore, reducing the taining Ionpure has achieved a 99.7%
risk of cross contamination of MRSA is a reduction against MRSA. The photographs Contact-
major concern in hospitals where out- are of the agar plates used for the bacteria WellsPlastics, EmeraM Wa3~Stone Business
breaks pose a serious risk to patients and count. They show clearly that there were Park, Stone, Staffordshire, ST15 OSR, UK.
can lead to the closure of wards in order to many bacteria recovered from the control Tel: +44 1785 817421

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P L E A S E I N S E R T 008 ON R E A D E R E N Q U I R Y C A R D Plastics Additives & Compounding October 2000

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